CN109234807A - A kind of stretchable crystalline semiconductor nano wire and preparation method thereof - Google Patents

A kind of stretchable crystalline semiconductor nano wire and preparation method thereof Download PDF

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Publication number
CN109234807A
CN109234807A CN201810614845.8A CN201810614845A CN109234807A CN 109234807 A CN109234807 A CN 109234807A CN 201810614845 A CN201810614845 A CN 201810614845A CN 109234807 A CN109234807 A CN 109234807A
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nano wire
stretchable
crystalline
crystalline semiconductor
silicon
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CN109234807B (en
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余林蔚
薛兆国
董泰阁
王军转
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Nanjing University
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Nanjing University
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Priority to EP18817489.0A priority Critical patent/EP3640374A4/en
Priority to PCT/CN2018/091544 priority patent/WO2018228543A1/en
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Priority to US16/714,724 priority patent/US20200118818A1/en
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Abstract

The present invention relates to a kind of stretchable crystalline semiconductor nano wire and preparation method thereof, the stretchable crystalline semiconductor nano wire has elongated main body, and for the nanowire diameter between 20-200 nanometers, the nano wire is crystalline inorganic semiconductor structure.The stretchable crystalline semiconductor nano wire is warp architecture, has multiple stretchable units in the axial direction, the multiple stretchable unit is sequentially connected, to form stretchable crystalline semiconductor nano wire.The present invention carries out being fabricated to spring structure crystalline nanometric linear array using modern micro-processing technology using the methods of IP-SLS nano wire that growth channel step guides in pecvd.Since such nano wire and guidance channels cross-section can be adjusted effectively, it can be removed and be transferred on other flexible substrates with further progress.The present invention, which prepares application aspect of the method for spring structure crystalline nanowire in flexible electronic field, sensor, wide prospect.

Description

A kind of stretchable crystalline semiconductor nano wire and preparation method thereof
Prioity claim
The application is the part of the CN201710450420.3 (publication number CN107460542A) submitted on June 15th, 2017 Continue application, and require its priority, entire contents are hereby incorporated herein by reference.
Technical field
The present invention relates to flexible extensible electronics and devices field, it is related to utilizing channels direct plane nano line on substrate Growing technology, by micro fabrication, production forms the system with the spring structure crystalline nanowire of flexible and stretchable nature Make method.The especially bullet of the integrated planar semiconductor nano wire preparation of the self-positioning self orientation growth of channels direct, transfer, electricity The method of spring structure crystalline nanowire.
Background technique
With the development of contemporary electronic display industry, flexible and stretchable electronic device (especially display device) is because more Easily meet practical application request and flexible material property itself, the side in modern science and technology, national economy and daily life Aspect face plays an increasingly important role, and in the research field, the growth technology of preparing of material has consequence.
Liquid-liquid phase-solid phase (SLS) growth mechanism: the mechanism of SLS growth is similar to VLS mechanism, the difference with VLS mechanism It is only that, in VLS mechanism growth course, required raw material are provided by gas phase；And in SLS mechanism growth course, it is required Raw material be to be provided from solution, in general, in the method commonly use low-melting-point metal (such as In, Sn or Bi) be used as hydrotropy Agent (fluxdroplet), the catalyst being equivalent in VLS mechanism.
Silica-base material is because of extensive industrial foundation, mature technique and semiconductor technology of preparing, and due to structoure of the human body Carbon-based material attribute it is similar, it is harmless, and nano silicone material is degradable, by silicon-based nano science and technology and flexible extensible Electronic field combines, and will obtain huge effectiveness.
The growth of the material of stretchable crystalline nanowire spring structure is flexible and stretchable electronic device basis, existing Technology does not have good method to go to solve.
Summary of the invention
In view of the above-mentioned problems, it is an object of the present invention to provide a kind of stretchable crystalline semiconductor nano wire and its preparation sides Method.Especially planar semiconductor nano-wire devices are prepared along particular pilot channel oriented growth, transfer and integrated approach.
According to an aspect of the present invention, the present invention provides a kind of stretchable crystalline semiconductor nano wires:
The stretchable crystalline semiconductor nano wire has elongated main body, and the nanowire diameter is in 20-200 nanometer Between, the nano wire is crystalline inorganic semiconductor structure.
The stretchable crystalline semiconductor nano wire is warp architecture, has multiple stretchable units, institute in the axial direction It states multiple stretchable units to be sequentially connected, to form stretchable crystalline semiconductor nano wire.
Further, the stretchable unit of stretchable crystalline semiconductor nano wire is arc-shaped, semicircle, half track type, Z One of shape, V-arrangement, M shape or multiple combinations.
Further, the length under maximum tension state is greater than 1.5 times of length under natural conditions, preferably 2 times with On, preferably 2.7 times.
In one embodiment, crystalline nanowire is grown, the nano wire is that the monocrystalline such as Si, SiGe, Ge or GaAs are received Rice noodles.
According to a further aspect of the invention, the present invention provides the preparation method of stretchable crystalline semiconductor nano wire, Include the following steps:
1) using including glass, titanium dioxide silicon wafer or silicon chip substrate, it is remaining to remove substrate surface；
2) in the step of substrate surface etching certain depth, and then along the specific guidance channel of step etching production；
3) growing method is guided by plane nano line, grows crystalline nanowire exactly along the guidance channel, In guidance channel one end vapor deposition catalytic metal film block, the start bit of formation initial point and nano wire as molten drop It sets；
4) metallic film is handled using the Reductive plasma for including hydrogen in a pecvd system, removes the oxygen on surface Change layer, and is allowed to form nano metal catalysed particulate of the diameter between tens nanometers to one microns；
5) noncrystal semiconductor layer of one layer of suitable thickness of deposit covering is as presoma medium；
6) it anneals in a vacuum or in non-oxidizing atmosphere growth, temperature is at 250 DEG C or more, so that molten drop starts Along guidance step movement, absorbs amorphous layer and deposit out the nanowire structure of crystalline state on the way.
Further, in step 1) silicon wafer be surface cover the dielectric layers such as silica or silicon nitride p-type or N-type Perhaps polysilicon chip glass is simple glass or quartz glass to monocrystalline, and polymer can be that can bear certain high temperature (> 350 DEG C) Processing, the flexible polymer mutually compatible with vacuum environment；The silicon dioxide substrates thickness is greater than 250nm.
Further, step 5) include: reuse PECVD system cover one layer of suitable thickness (several nanometers are received to several hundred Rice) noncrystal semiconductor layer as presoma dielectric layer；For growth crystal silicon, brilliant germanium or crystalline state germanium-silicon alloy nano wire, phase It should be using amorphous silicon, amorphous germanium and amorphous germanium silicon layer as presoma；And other semiconductor materials are then used corresponding non- Brilliant material film is as presoma.
In one embodiment, further include step 7): electrode is prepared by photoetching and evaporation coating technique.
In one embodiment, further comprising the steps of:
Step 8) is by etch liquids, so that nano wire and substrate are detached from；
Step 9) is transferred to the spring nano-wire array of disengaging in flexible substrate, and used flexible substrate, which can be, appoints Anticipating has the substrate of tensile property.
Substrate used in growing, which can be p-type or n type single crystal silicon substrate, surface, silicon dioxide layer；Can be p-type or There is silicon dioxide layer on N-type polycrystalline silicon piece, surface；It is also possible to simple glass, the amorphous body substrate such as quartz glass.
Guidance channel is made by chemical wet etching method；Wherein lithographic method wet etching: potassium hydroxide (KOH), hydrogen The alkaline corrosions systems such as sodium oxide molybdena (NaOH) are also possible to hydrofluoric acid+nitric acid (HF+HNO3), hydrofluoric acid+nitric acid+acetic acid (HF+ The sour corrosions system such as HNO3+CH3COOH), can also be ethylene diamine pyrocatechol (EthyleneDiaminePyrocatechol) systems such as；Or use dry etching, i.e., it is performed etching using ICP-RIE.
Metal electrode uses PT (12nm)-AL (80nm) system, can be Ti-Au system, is Ni metal, and metal contact is equal Contact performance is improved using rapid thermal annealing process.Thermal evaporation system, magnetic control sputtering system or electron beam evaporation system can be used System.
Corrode substrate surface using etch liquids, so that spring structure crystalline nanowire and substrate are detached from, completion is facilitated to turn It moves.
Spring structure crystalline nanowire is the flexible high performance device with height tensility.
Beneficial effects of the present invention
The present invention is utilized modern micro- using the methods of IP-SLS nano wire that growth channel step guides in pecvd Processing technology carries out being fabricated to spring structure crystalline nanometric linear array.IP-SLS method can be with growth plane nano wire, in conjunction with platform Rank channels direct technology can grow the planar semiconductor monocrystal nano line array of high quality, specific shape.Pass through photoetching Self-positioning, the self orientation of nanowire growth are achieved that after the catalyst area of guidance channel and positioning that erosion technology is formed.By It can effectively adjust, (such as etch removing) can be removed with further progress and shift in such nano wire and guidance channels cross-section To on other flexible substrates.Since there is electrode connection at nano-wire array both ends, it may be convenient to carry out the integrated of device and make With.The present invention prepare application aspect of the method for spring structure crystalline nanowire in flexible electronic field, sensor have it is wide Prospect.
The present invention utilizes the characteristic of the bootable growth of plane nano line for the first time, the super flexible nano duct diatom of achievements exhibition Shape design and stretchable Crystalline Semiconductors nanowire structure.By taking crystal silicon as an example, crystal silicon itself is non-stretchable also frangible, and crystal silicon is thin Film not can be used directly in stretchable electronic device applications.It, can be by the crystal silicon semiconductor of existing maturation by the invention technology Technical matters is extended to emerging flexible electronic application field, for the device property and stability that flexible electronic device is substantially improved Key technology basis is provided.
Detailed description of the invention
Fig. 1 is spring structure crystalline nanowire preparation process flow chart；
Fig. 2 is spring structure crystalline nanowire Array Design schematic diagram；In Fig. 2, spring structure crystalline nanometric linear array is set Schematic diagram is counted, wherein blue (dark color) region is that catalyst area (a) (b) (c) (d) respectively indicates four kinds of different spring shapes songs Line；
Fig. 3 is spring structure crystalline nanowire SEM shape appearance figure；In Fig. 3, spring structure crystalline nanowire SEM shape appearance figure, (a) (b) (c) (d) respectively indicates four kinds of different ratios.
Fig. 4 is spring structure crystalline silicon nanowires electric property figure.
Fig. 5 (a) and (b) are the SEM mechanical stretch in situ and synchronous electrical testing of a kind of stretchable silicon nanowires of citing, Fig. 5 (c) is synchronizing potential test result figure；Stretchable silicon nanowires is stretched to the elastic deformation limit thus by Fig. 5 (d) and (e) 270% and can restore completely process SEM figure.
Specific embodiment
To be more clearly understood that the purpose of the present invention, technical solution, effect and advantage, below in conjunction with specific example, to this hair It is bright to carry out further explanation in detail.
As shown in Fig. 2, the present invention provides a kind of stretchable crystalline semiconductor nano wire, the stretchable crystalline semiconductor Nano wire has elongated main body.The stretchable crystalline semiconductor nano wire is warp architecture, is had in the axial direction multiple Stretchable unit, the multiple stretchable unit are sequentially connected, to form stretchable crystalline semiconductor nano wire.
Further, for the nanowire diameter between 20-200 nanometers, the nano wire is crystalline inorganic semiconductor Structure.
As shown in Fig. 2, crystalline nanowire Array Design schematic diagram, wherein blue (dark color) region is catalyst area (a) (b) (c) (d) respectively indicates four kinds of different spring shape curves；From figure it is found that the nano wire is warp architecture, in axial side To with multiple stretchable units interconnected, the stretchable unit is arc-shaped, semicircle, one in half track type Or it is multiple.
Further, the stretchable unit of stretchable crystalline semiconductor nano wire is arc-shaped, semicircle, half track type, May be Z-shaped, V-arrangement, M shape (not shown), or in which one or more combinations.
Further, the length under maximum tension state is greater than 1.5 times of length under natural conditions, preferably 2 times with On, preferably 2.7 times.
In one embodiment, crystalline nanowire is grown, the nano wire is that the monocrystalline such as Si, SiGe, Ge or GaAs are received Rice noodles.
Substrate used in growing, which can be p-type or n type single crystal silicon substrate, surface, silicon dioxide layer；Can be p-type or There is silicon dioxide layer on N-type polycrystalline silicon piece, surface；It is also possible to simple glass, the amorphous body substrate such as quartz glass.
Fig. 3 is spring structure crystalline nanowire SEM shape appearance figure, the spring structure crystalline nanowire SEM shape actually prepared Looks figure, (a) (b) stretchable unit is arc-shaped structure, (c) (d) stretchable unit is half track type structure.(a)(b)(c)(d) Respectively indicate four kinds of different ratios.
Fig. 4 is the electric property figure for the spring structure crystalline silicon nanowires prepared.
If Fig. 5 (a) (b) is citing, in situ in scanning electron microscope, under the operation of mechanical probes, mechanical stretch wherein one Kind silicon nanowires simultaneously synchronizes electrical testing to it.Shown in test result such as Fig. 5 (c), show in silicon nanowires tensile elasticity During deformation, electrical properties are stablized.
As shown in Fig. 5 (d) (e), such silicon nanowires can length by mechanical stretch to the limit, under maximum tension state Degree is greater than under the 270% of length under natural conditions, still keeps elastic deformation, after release, can resile.
According to a further aspect of the invention, as shown in Fig. 1, it is linear based on plane nano line that the present invention provides one kind The preparation method of the stretchable crystalline semiconductor nano wire of design and guidance, characterization step include:
1) with glass, titanium dioxide silicon wafer, perhaps the substrates such as silicon wafer carry out the substrates such as glass, titanium dioxide silicon wafer or silicon wafer Standardization cleaning, removes surface organic matter and metal residues；
2) step using photoetching technique (or picture on surface lithographic technique) in substrate surface etching certain depth, this guidance The linear of step freely easily can be designed and define；It, will in order to realize stretchable flexible Crystalline Semiconductors channel structure Step is linear to be designed to non-directional curved spring or zigzag serpentine channels shape array, passes through chemical wet etching skill on substrate Art produces the guidance channel array of depth about 150 ± 10nm (being no more than 350nm) spring shape, and the list of more space relaxation Line connection divides shape bending Two dimensional Distribution structure etc.；
3) growing method is guided by plane nano line, makes the crystalline nanowire of diameter about 120 ± 10nm diameter accurately It is grown along the guidance channel, forms nano wire spring array；I.e. by photoetching lift-off or mask plate technique, drawing Guide channel road one end vapor deposition catalytic metal film block, the initial position of formation initial point and nano wire as molten drop；
4) metallic film is handled using Reductive plasmas such as hydrogen in a pecvd system, removes the oxide layer on surface, And it is allowed to form nano metal catalysed particulate of the diameter between tens nanometers to one microns；
5) noncrystal semiconductor layer of one layer of suitable thickness of deposit covering is as presoma medium；
6) it anneals in a vacuum or in non-oxidizing atmosphere (temperature is at 250 DEG C or more) growth, so that molten drop is opened Begin to absorb amorphous layer along guidance step movement and deposit out the nanowire structure of crystalline state on the way；
7) electrode is prepared at the both ends of nano wire spring array by photoetching and evaporation coating technique；
8) by etch liquids nanometer wire spring and substrate are detached from；
9) the spring nano-wire array of disengaging is transferred in flexible substrate, stretchable nano wire bullet can be produced Spring can be widely applied to flexible electronic field.It is poly- that flexible nano wire spring or dependency structure can be transferred to flexible extensible It closes on object substrate and (by sample surfaces spin coating thin film, and sacrifice layer corrosion is cooperated to shift, and directly utilize nano-machine Manipulation is selected in picking).
Further, in step (1) substrate described in its feature can for silicon wafer, glass, potsherd and can high temperature resistant to 350 DEG C polymer substrate.The silicon dioxide substrates are general silica substrate, and thickness is greater than 250nm.Silicon wafer can also be table Face covers the p-type or N-type monocrystalline or polysilicon chip of the dielectric layers such as silica or silicon nitride, glass be simple glass or Person's quartz glass, polymer can be handled for that can bear (> 350 DEG C) of certain high temperature, the flexible polymer mutually compatible with vacuum environment.
Further, in step 3), lithography alignment technology catalyst area on the position of channel is reused, by flat Face nano wire guides growing method, makes the crystalline nanowire of diameter about 130 ± 10nm diameter exactly along the guidance channel Growth forms the nano wire of spring shape；In is deposited, Sn metal is the gold for guiding channel specific position to form tens nanometers Belong to film figure；Plasma treatment technique is utilized in a pecvd system, is handled in 350 DEG C, power 2-5W, makes metal Film contracting ball forms diameter in several hundred nanometers to the quasi- catalyzing nano-particles between several microns；Reuse PECVD system covering one The amorphous silicon of the amorphous silicon (several nanometers are arrived several hundred nanometers) of layer suitable thickness is as presoma dielectric layer；Under vacuum, 350 Anneal in DEG C environment, using IP-SLS growth pattern so that nano wire from catalyst area along guidance channel growth, formed simultaneously Obtain the nano wire of spring structure.
Further, in step (3) catalytic metal described in its feature can for low-melting-point metal indium, tin, gallium, lead, bismuth etc., with And the noble metals such as their alloy and oxide material, and the gold, silver, the copper that match with the crystalline state nano-material grown.
Further, its characterization step includes: to define plane in photoresist layer using photoetching technique first to receive in step (2) The guidance step of rice noodles is linear, then will be schemed using reactive plasma (RIE) or induction plasma (ICP) lithographic technique Shape etches among substrate downwards, and etching depth arrives several hundred nanometer ranges several；
In one embodiment, guidance channel is made by chemical wet etching method；Wherein lithographic method wet etching: hydrogen The alkaline corrosions systems such as potassium oxide (KOH), sodium hydroxide (NaOH), be also possible to hydrofluoric acid+nitric acid (HF+HNO3), hydrofluoric acid+ The sour corrosions systems such as nitric acid+acetic acid (HF+HNO3+CH3COOH), can also be ethylene diamine pyrocatechol (EthyleneDiaminePyrocatechol) systems such as；Or use dry etching, i.e., it is performed etching using ICP-RIE.
In one embodiment, wherein spring shape crystalline nanowire, the crystalline substances such as nano wire Si, Ge, SiGe, GaAs are grown Body material.Using any shape and structure with tensile property, crystalline nanometric linear diameter is in 20-180nm.
Further, its characterization step includes: using photoetching or mask plate technique, using metal catalytic in step (3) Layer is urged by the techniques such as thermal evaporation, magnetron sputtering, electron beam transpiration, pulsed laser deposition and atomic layer deposition, vapor deposition indium, tin etc. Change metal layer thin film, is allowed to be formed several microns of metal diaphragm area, and in guidance channel certain start position and guidance step Intersect.
It further, include: in a pecvd system using plasma treatment technique, at 200 DEG C to 450 in step (4) Handled within the scope of DEG C, between 0.2-100 watts of power, make metal film contracting ball formed diameter tens nanometers to several microns it Between catalyzing nano-particles；
Further, in step (5) its characterization step include: reuse PECVD system cover one layer of suitable thickness it is (several Nanometer arrive several hundred nanometers) noncrystal semiconductor layer as presoma dielectric layer.Growth crystal silicon, brilliant germanium or crystalline state germanium silicon are closed Nanowires of gold, accordingly using amorphous silicon, amorphous germanium and amorphous germanium silicon layer as presoma.And other semiconductor materials are then adopted Use corresponding non-crystalline material film as presoma.
Further, in step (6): being directed to different semiconductor materials, the growth temperature of plane nano line is selected at 300 DEG C To between 600 DEG C.Nanowire growth process can carry out under inert gas, reducibility gas or vacuum condition.
Further, in step (7): the plane nano line grown is linear to be controlled by guidance step edge, can be obtained Programmable Design non-rectilinear flexural spring or zigzag serpentine channels and single line connection divide shape be bent Two dimensional Distribution knot Structure, to realize stretchable crystal silicon semiconductor nano wire channel.
In yet another embodiment, Alignment Design and guidance growing technology based on plane nano line, realize that crystalline state is partly led The preparation method of body (including silicon, germanium etc.) stretchable electronic device.Using conventional lithographic, lithographic technique or other templates and Surface-micromachining process makes the guidance step of specific morphology on glass or crystalline silicon substrate, (utilizes amorphous with noncrystalline membrane Silicon, amorphous germanium and other amorphous inorganic semiconductor materials) it is used as presoma, it is catalyzed using metal (indium, tin, gallium, bismuth etc.) Particle absorb noncrystal membrane, postpone guide step movement during, grow corresponding plane crystalline state (simple substance or conjunction Gold) nanowire structure.Due to guidance step can free Programming, completely may be used so linear (line-shape) can be customized Control, regular crystalline state nano-wire array, and then prepare the Crystalline Semiconductors nanowire structure with super tensility.This technology The Crystalline Semiconductors material nano channels such as the crystal silicon with high tensility can be achieved, maintain the excellent of crystal semiconductor material Electricity is modulated and device stability characteristic (quality), so it is (such as stretchable that high performance flexible semiconductor electronic application may be implemented Logic transistor, display control and driving element, the emerging fields such as sensing and artificial skin).
Specifically, a kind of technology of growth, the transfer of the crystalline nanowire of spring structure.It is the orientation under specific channel The method of growth, transfer, its step are as follows:
1) by soda acid hot solution or respectively by acetone, alcohol, deionized water ultrasonic treatment to covering oxide layer Crystalline substrates are handled, and the impurity of removal surface attachment exposes crystal clean surface.
2) channel array is grown using the guidance of chemical wet etching technical definition spring structure, reuses lithography alignment technology Catalyst area is defined on the specific position of channel.Certain depth is formed using photoetching technique (or picture on surface lithographic technique) Guidance step；
3) by photoetching lift-off or mask plate technique, in guidance channel one end vapor deposition catalytic metal film Block；In is deposited, Sn metal is allowed to exist only in the metal film that guidance channel specific position forms tens nanometers by liftoff Pattern；
4) plasma treatment technique is utilized in a pecvd system, is handled in 350 DEG C, power 2-5W, makes metal Film contracting ball forms diameter in several hundred nanometers to the quasi- catalyzing nano-particles between several microns；
5) amorphous silicon that PECVD system covers the amorphous silicon (several nanometers are arrived several hundred nanometers) of one layer of suitable thickness is reused As presoma dielectric layer.
6) it anneals in a vacuum or in non-oxidizing atmosphere (temperature is at 280 DEG C or more) growth, so that molten drop is opened Begin to absorb amorphous layer along guidance step movement and deposit out the nanowire structure of crystalline state on the way；Especially under vacuum, It anneals in 350 DEG C of environment, using IP-SLS growth pattern, so that nano wire is raw along particular pilot channel from catalyst area It is long, form and obtain the nano wire of spring like.
7) lithography alignment technology and metal evaporation technology are utilized again, cost electrode at the both ends of nano wire spring array.
8) sample surfaces are performed etching using HF, so that nano wire and substrate are detached from.
9) the nano wire spring array being detached from substrate is transferred in flexible substrate.Flexible nano wire spring or related knot Structure, which can be transferred in flexible extensible polymer substrate, (by sample surfaces spin coating thin film, and cooperates sacrifice layer corrosion Transfer, and directly manipulation is selected using nano-machine picking).
Further, the guidance channel of depth about 200nm, the guidance channel of spring structure are produced by chemical wet etching (see Fig. 1), wherein spring structure can be any bending shape with stretchable nature, and the distance between node and node can Think 200nm~50um.The lithographic method of channel can use wet etching: the alkalinity such as potassium hydroxide (KOH), sodium hydroxide (NaOH) System is also possible to the acid body such as hydrofluoric acid+nitric acid (HF+HNO3), hydrofluoric acid+nitric acid+acetic acid (HF+HNO3+CH3COOH) System, can also be the systems such as ethylene diamine pyrocatechol (EthyleneDiaminePyrocatechol)；It is also possible to dry etching System is performed etching using ICP-RIE.
Further, the etch liquids that transfer step uses, which can be, any can corrode silica and slowly or be stale-proof Lose the liquid of crystalline nanowire.Flexible substrate used in shifting can be any substrate with tensile property.
Further, the nano wire of planar growth can be Si, SiGe, Ge, the plaine single crystals nano-wire array such as GaAs, directly Diameter is distributed between 20~200nm.
Further, metal electrode is made using photoetching evaporation coating technique, thermal evaporation system, electron beam evaporation system can be used With magnetic control sputtering system etc., metal electrode contact uses PT (12nm)-AL (80nm) system, can be Ti-Au system, can be Ni metal, metal electrode contact improve contact performance using rapid thermal annealing process.
One more specific real-time example: 300nmSiO2The preparation of oxide layer substrate upper spring structure crystal nano wire, including with Lower step:
1) 300nmSiO2 oxide layer substrate (silicon wafer through surface oxidation) is used, uses acetone, alcohol, deionization respectively Water ultrasonic treatment, the impurity of removal substrate surface attachment.Pure monocrystalline or polysilicon silicon wafer can be used in silicon wafer.
2) it by there is mask lithography technology to define spring structure pattern in substrate surface, is etched using ICP-RIE on surface Channel is formed, forms the array of bioprobe channel after cleaning photoresist.
3) it in a pecvd system, is allowed to form diameter using plasma treatment technique under 1-50W power and be received several hundred Rice arrives the catalyzing nano-particles between several microns；Catalyzing nano-particles of the diameter at several hundred nanometers are formed at a temperature of 350 DEG C.
4) continue to cover the amorphous silicon layer of one layer of suitable thickness in a pecvd system as presoma dielectric layer；300℃- The amorphous silicon layer of one layer of suitable thickness is covered at 400 DEG C.Annealing exists in vacuum or in the non-oxidizing atmospheres such as hydrogen, nitrogen At 400 DEG C, the amorphous silicon of surrounding is can be absorbed in catalysis drop after being activated, and goes out plane silicon nanowires so as to induced growth, Nano wire can form required channel along guidance trench sidewalls oriented growth simultaneously.
5) in atmosphere of hydrogen using the amorphous silicon 15 minutes of plasma treated surface remnants until surface color recovery Normal color.
6) lithographic definition electrode pattern is reused, using electron beam evaporation technique, 12nm titanium and 60nm gold is deposited, later The photoresist and remaining metal washed.
7) be spin-coated on substrate surface using PMMA, reuse the HF solution etches substrate of 4% concentration, make PMMA film with Crystalline state nano wire spring array and substrate are detached from.
8) it is got using the spring structure crystalline nanowire of PDMS film the PMMA film being detached from substrate and above, Solvent is reused PMMA Film Fractionation, spring structure crystalline nanowire has been transferred on flexible substrate PDMS.
As described above, the present invention can be realized preferably.For a person skilled in the art, do not depart from it is of the invention These embodiments are changed in the case where principle and spirit, modifies, replace, integrating and modification still falls within protection of the invention In range.The part for not carrying out specified otherwise or restriction in the present invention is all made of prior art implementation.

Claims (10)

1. a kind of stretchable crystalline semiconductor nano wire, it is characterised in that: the nano wire has elongated main body, the nanometer For linear diameter between 20-200 nanometers, the nano wire is crystalline inorganic semiconductor structure.
2. stretchable crystalline semiconductor nano wire according to claim 1, it is characterised in that: the nano wire is bending knot Structure has multiple stretchable units in the axial direction, and the multiple stretchable unit is sequentially connected, to form stretchable crystal Semiconductor nanowires.
3. stretchable crystalline semiconductor nano wire according to claim 2, it is characterised in that: the stretchable unit is circle One of arc, semicircle, half track type, Z-shaped, V-arrangement, M shape or multiple combinations.
4. stretchable crystalline semiconductor nano wire according to claim 2, it is characterised in that: the nano wire maximum tension Length under state is greater than 1.5 times, preferably 2.7 times of length under natural conditions.
5. according to the described in any item stretchable crystalline semiconductor nano wires of claim 2-4, it is characterised in that: the nano wire It is Si, SiGe, Ge or GaAs monocrystal nanowire.
6. a kind of preparation method of stretchable crystalline semiconductor nano wire as described in claim 1, which is characterized in that including such as Lower step:
1) using including glass, titanium dioxide silicon wafer or silicon chip substrate, it is remaining to remove substrate surface；
2) in the step of substrate surface etching certain depth, and then specific guidance channel is produced along step etching；
3) growing method is guided by plane nano line, grows crystalline nanowire exactly along the guidance channel, is drawing Guide channel road one end vapor deposition catalytic metal film block, the initial position of formation initial point and nano wire as molten drop；
4) metallic film is handled using the Reductive plasma for including hydrogen in a pecvd system, removes the oxide layer on surface, And it is allowed to form nano metal catalysed particulate of the diameter between tens nanometers to one microns；
5) noncrystal semiconductor layer of one layer of suitable thickness of deposit covering is as presoma medium；
6) anneal in a vacuum or in non-oxidizing atmosphere growth, temperature at 250 DEG C or more so that molten drop start along Step movement is guided, amorphous layer is absorbed and deposits out the nanowire structure of crystalline state on the way.
7. stretchable crystalline semiconductor nanowire preparation method according to claim 6, silicon wafer covers in step 1) for surface Perhaps polysilicon chip glass is simple glass or stone to the p-type or N-type monocrystalline of the dielectric layers such as lid silica or silicon nitride English glass, polymer can be handled for that can bear (> 350 DEG C) of certain high temperature, the flexible polymer mutually compatible with vacuum environment；It is described Silicon dioxide substrates thickness is greater than 250nm.
8. stretchable crystalline semiconductor nanowire preparation method according to claim 6, step 5) includes: to reuse PECVD system covers the noncrystal semiconductor layer of one layer of suitable thickness as presoma dielectric layer；For growth crystal silicon, brilliant germanium or Crystalline state germanium-silicon alloy nano wire, accordingly using amorphous silicon, amorphous germanium and amorphous germanium silicon layer as presoma；And it is partly led for other Body material is then using corresponding non-crystalline material film as presoma.
9. stretchable crystalline semiconductor nanowire preparation method according to claim 6, further includes step 7): passing through photoetching Electrode is prepared with evaporation coating technique.
10. the preparation method of stretchable crystalline semiconductor nano wire according to claim 9, characterized in that further include with Lower step:
Step 8) is by etch liquids, so that nano wire and substrate are detached from；
Step 9) is transferred to the spring nano-wire array of disengaging in flexible substrate, and used flexible substrate can be any tool There is the substrate of tensile property.
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